Emulsions



Patented July 10, 1945 EMULSIONS William C. Griflin, Tamaqua, Pa.,assignor to Atlas Powder Company, Wilmington, DeL, a

corporation of Delaware No Drawing. Application May 27, 1941, Serial No.395,392

18 Claims.

The present invention relates to improvements in emulsions.

An object of the invention is to provide a new emulsifier composition.

Another object is to provide an emulsifier composition which dispersesreadily in water.

Another object is to provide an emulsifier composition which is capableof forming stable emulsions of waxes and water.

Another object is to provide emulsions of oil and water comprising mynovel emulsifier composition.

A further object is to provide emulsions which are stable to dilutionwith hard water.

A still further object is to provide wax emulsions of improvedproperties.

This application is in part a continuation of my copending applicationSerial Number 367,017, filed November 25, 1940.

Emulsions have long been made with long chain fatty acid partial estersof polyhydric alcohols or other polyhydroxy materials. There aredefinite advantages attending the use of emulsifiers of this type. Inmany instances, however, it has been found impossible to prepareemulsions of desirable oleaginous materials with these emulsifiers.These partial esters are also imperfect emulsifiers in that they arepractically insoluble and very difiicult to disperse in water, many ofthem being impossible to disperse. It has been proposed to improvedispersibility of these esters by including in them, or in the water, asoap or soap-forming alkaline substance. In some cases an improvementcan be noted but the disadvantages of soap as an emulsifier are thenencountered.

I have found that in accordance with the present invention, emulsifyingcompositions of improved properties result from the combination of alipophilic long chain fatty acid partial ester of a. polyhydroxylicmaterial and a highly hydrophilic hydroxy-polyoxyethylene ether of apartial ester of said type. The natures of these ingredients will bedescribed more in detail hereinafter. By combining materials of thesetypes I am able to prepare emulsifiers which are much more readilydispersible in water than the partial esters by themselves. Furthermore,the combinations are emulsifiers of much greater versatility than thepartial esters by themselves. The highly hydrophilichydroxy-polyoxyethylene ethers of the partial esters, by themselves, arenot particularly efficient emulsifiers for most purposes. Thecombination of these two types of ingredients has properties notpossessed by either of them alone.

My combination emulsifiers have the property of resistance to hardwater. In this respect particularly they are outstanding by comparisonwith the partial esters rendered more dispersible by the addition ofsoaps.

Emulsions of an oil phase, water, and my combination emulsifier havemany uses and advantages. The novel emulsifying composition makes itpossible to prepare usefully stable emulsions of oils and waxes whichare generally classified as very difilcultly emulsifiable. The emulsionsaccording to this invention can be prepared in a concentrated form andlater diluted, even with hard water, to the desired degree withoutdestroying the emulsion.

A particular advantage of my invention is in the use of the combinationemulsifiers to emulsify waxes, particularly paraffin waxes. Theresulting emulsions exhibit very desirable properties and have manyuses.

Waxes of various types have very wide industrial applications,particularly in the field of coatings. For example, paraflin wax is avery valuable and readily available coating agent for paper, paperboard, composition board of various kinds, cloth, textiles and the likein which uses the paraffin acts to reduce absorbency, to waterproof, toimprove the feel, etc. Another use of paraffin is in the field oflaundry waxes in which paraffin, either alone or mixed with othermaterials, is incorporated into starch used in laundering for thepurpose of imparting a lubricant for ironing and also to improve theappearance of the ironed fabric.

In the field of coating, it is recognized as a definite advantage to beable to use the paraflln in the form of an emulsion in water. Suchemulsions are economical to prepare and use and the vehicle is one whichdoes not involve expense nor is it undesirable for application to mostobjects. In the past, however, the usual emulsifiers for parafiin Waxeshave been soaps, either alkali metal soaps or soaps of the strongorganic nitrogen bases such as triethanolamine. The emulsions producedfrom soaps have numerous defects among which is the outstandingdisadvantage that they cannot be diluted with hard water without causinga precipitation of the soap and consequent breaking of the emulsion.

In the field of the laundry waxes and the like, it is desirable toprepare a solid dispersible wax composition, which can be added to a hotwater solution of starch, and used for wax-starching fabrics in theusual manner. In the past the wax compositions have been prepared byincorporating such materials as natural emulsifying waxes with theparafiin wax, but such waxes are not entirely satisfactory andfurthermore, being natural products, are subject to wide variation inquality, price and quantity available.

For convenience in description my emulsifiers will be describedgenerally as a mixture of type A and type B emulsifiers.

In type A are included, in accordance with the invention, lipophilicpartial long-chain fatty acid esters of poly-hydroxylic organiccompounds. Type B includes, in general, the highly hydrophilichydroxy-polyoxyethylene ethers of type A compounds.

I have used the adjective lipophilic" to indicate the property of apolar compound (partial ester of polyhydroxy substance) which has goodoil-solubility or dispersibility and no, or very little,water-solubility. The term highly hydrophilic" is used to signify acompound which is from readily dispersible in to completely misciblewith water.

More particularly, the type A esters are obtained by combiningwater-insoluble organic acids, especially fatty acids having at least 12carbon atoms, such as those obtainable by hydrolysis of natural fats,oils, and waxes, or from the oxidation of paramns, with suitablealiphatic polyhydroxylic compounds. Water-insoluble cyclic acids, suchas naphthenic acids, can also be used in the preparation of the partialesters. Suitable polyhydroxylic compounds comprise ethylene glycol;diand tri-ethylene glycol; glycerol and polyglycerols; pentaerythritol;pentitols; hexitols and the cyclic inner ethers thereof; cyclitols suchas inositol; aligosaccharides such as glucose, sucrose and lactose; theglycol and lower polyglycol ethers of such polyhydroxylic compounds; and

other polyhydric compounds of typically hydrophile character.

I have found that very good results are obtained from the esters of themixed cyclic inner ethers of the hexitols, such as sorbitans andsorbides from sorbitol, or mannitans and mannides from mannitol.

In these type A partial esters, monoesters tend to be the mostefi'ective.

Furthermore, for esters of the polyhydroxylic compounds derivable fromthe hexitols, I have found that the ratio of hydroxyl value to estervalue for optimum performance lies between 3 and 1, and preferablybetween 3 and 1.5.

These partial esters may be prepared by any one of several knownmethods; such as by direct esterification of the polyhydroxy materialwith free fatty acid or by alcoholysis of naturally occurring esterswith polyhydroxy material, using suitable catalysts. With heat-sensitivepolyhydroxylic compounds, the acid chlorides and pyridine or othersuitable base may be employed.

For the preparation of my preferred type A esters, I use, as startingmaterials, mannitoi, sorbitol, or the mixture of sorbitol and hexanepentols obtainable by the reduction of glucose, and react thesepolyalcohols with the organic acids under conditions leading to theformation of the corresponding cyclic inner ethers and theesterification thereof by the acid. Alternatively, I may preform theinner ethers or mixtures thereof and esterify by known methods. Thefollowing illustrate the preparation of my preferred type A esters:

Example 1 182 g. (1 mol) of mannitol and 256 g. (1 mol) palmitic acidwere heated together in the presence of .05% NaOH based upon totalreactants as catalyst. An atmosphere of inert gas was maintained in thereaction vessel and the ingredients were thoroughly stirred. Thetemperature was brought to 240 C. in 70 minutes and held at that valuefor 5 hours. 13 g. of decolorizing carbon were added,30 minutes beforethe end of the reaction period and the batch filtered. The resultingproduct, chiefly mannitan monopalmitate, was a yellow, waxy solidmelting at 42-45 C., insoluble and diflicultly dispersible in water. The

hyd oxyl value was 355 and the ester value was 146.

Example 2 182 g. (1 mol) of mannitol and 284 g. (1 mol) stearic acidwere heated together in the presence of .05% NaOH as catalyst. Anatmosphere of inert gas was maintained in the reaction vessel and theingredients were thoroughly stirred. The temperature was brought to 250C. in '70 minutes and held at that value for 5 hours.

9 g. decolorizing carbon were added 30 minutes before the end of thereaction periodand the batch filtered. The resulting product, chieflymannitan monostearate, was a light gray, brittle, waxy material, meltingat 45-48 C., insoluble and undispersible in water. The hydroxyl valuewas 301, and the ester value was 150.

The type B material, the second component of m novel combinationemulsifier, comprises the highly hydrophilic and preferably the readilywater-soluble hydro'xy-polyoxyethylene ethers of the type A partialesters. These ethers can be prepared by methods known to those skilledin this art. Thus, I may etherify the partial ester by heating with apreformed polyethylene glycol, or, more conveniently, by reacting theester with ethylene oxide in the presence of suitable catalysts.

The ether-ester becomes more hydrophilic with increase in the number ofC2H4O units per mol. I have found it particularly advantageous to reactthe ester with from 10 to 30.mols of ethylene oxide. The longer thefatty acid radical in the ester and the greater the degree ofesterification (mono-, di-, etc., ester) the more C2H4O units requiredfor optimum results.

The following examples illustrate the preparation of such ethers:

E :cample 3 80 lbs. (V5 mol) of the product of Example 1 were melted andintroduced into a stirringautoclave. Heat was applied and when thetemperature reached C., 72.5 g. of dry sodium methylate were added ascatalyst.

When the temperature reached 110 0., introduction of liquid ethyleneoxide was started. In the course of 2.5 hours 176 lbs. (4 mols) ethyleneoxide were added, the temperature being controlled within the range ofto C. by the use of a cooling coil in the autoclave. The temperature wasmaintained at 105 to 110 C..until the ethylene oxide was consumed asindicated by return of the pressure to atmospheric.

The product was transferred to a vacuum kettle and blown withsuperheated steam (at C.) under 10 mm. pressure with good agitation for30 minutes. 2% of activated carbon were added and heating continued for15 minutes after which the batch was filtered.

The weights of starting materials taken correspond to 20 mols ethyleneoxide to 1 mol of ester, calculated as mannitan monopalmitate.

The product was an odorless, amber slightly viscous liquid, misciblewith water in all proportions at room temperature.

" Example 4 430 g. of the product of Example 2 were introduced into apressure reaction bomb. 22 g. sodium methylate were added and themixture chilled. 440 g. liquid ethylene oxide were added and the bombcapped. The reaction vessel was put in a rocking device and heat appliedgradually until reaction set in as indicated by a rapid rise intemperature. The temperature was maintained at 100 C. and the maximumpressure developed was 138 lbs/in. After the main reaction had subsided,the temperature was maintained at 100 C. until the pressure had droppedto atmospheric. The total time at 100 C. was hours. The product wastreated with superheated steam according to the process of Example 3.The final product was a gelatinous solid having a hydroxyl value of 193and an ester value of 75. The compound contained approximately molsethylene oxide per mol of original ester (calculated as mannitanmonostearate). This material was readily dispersible in water at roomtemperature.

The proportion of the A and B types of emulsiflers in my combination issusceptible of wide variation. It will be understood by those skilled inthe art that a combination which is best suited for one set ofconditions may not be the optimum combination for a different set ofconditions. The character of the oil phase, the character of the aqueousphase, the particular combination of A and B employed, conditions of usesuch as dilution, temperature, degree of agitation, etc., are factors tobe considered in determining the best combination in a given case.

It is useful in many cases to express the proportion of A and B in termsof the ratio of C2H4O units in B to the total ester in A and B. For agiven set of conditions the limiting values for the ratio are readilydeterminable and a range thereby delineated.

This ratio may be calculated from the weights and molecular weights of Aand 3 according to the following formula:

M a W511 -WW:

wherein Ma=molecular weight of A Mb=molecular weight of B We. Wb=weightsof A and B respectively n=number of C2H4O units per mol of B In the caseof the waxes the preferred ratio lies in the range 1.5 to 9. Where thewater contains another emulsifier or suspending agent the ratio may belower. In the case of laundry starching wax compound the oil phase mustbe emulsifiable in a hot starch solution. In such a case it has beenfound that still lower values for the ratio are operative.

Using hexitan or hexide derivatives for emulsifying hard paraflln waxesI have found preferable a composition in which the value for this ratiolies between 4 and 5. waxes mixed with other materials such as fats canbe emulsified with compositions havin other optimum values for thisratio.

Emulsions of oils or fats can generally be prepared within the ratiovalues 1.5 to 9 but for specific cases variations may be desirable.

It will be readily apparent to those skilled in the art that the amountof the combination emulsifier in a given emulsion will depend on thekind of material to be emulsified, the aqueous phase, and the conditionsof use. The subsequent examples illustrate some of the possiblevariations in the amount of combination emulsifiers.

The waxes which I contemplate emulsifyin correspond to the broaddefinition of paraffin wax as used in the petroleum industry and alsoinclude similar waxes such as the fossil waxes and mineral waxes foundin nature as distinguished from those produced in the refining ofpetroleum. Thus, among the petroleum paraffin waxes I can Softer waxesand use an ordinary white wax such, for example, as the materialmarketed by Socony-Vacuum Oil Company under the trade-mark "Parasealwhich is an ordinary household paraflin wax. Another petroleum paraffinthat I can use is crude scale wax. Further waxes which can be used arethose of the microcrystalline type obtained in the refining ofpetrolatum such as that sold by Socony- Vacuum Oil Company under thename Cerese Wax AA." Many other petroleum paraflin waxes are known andwill be found applicable in my invention.

Among the waxes of nonpetroleum origin may be mentioned ozokerite,ceresin, and montan waxes. These natural or fossil waxes have physicalproperties approximating those of the petroleum paraflln waxes and maybe substituted for them in many emulsions.

The Waxes listed above are not true waxes in the strict chemical senseof the word but are generally known by this term in the trade. I mayalso use the true waxes such as beeswax, or carnauba wax, but the trueanimal and vegetable waxes in general are more easily emulsified thanthe mineral types of waxes and do not present as difficult a problem.Whenever I use the word wax without modification it is intended toinclude both the waxes properly so-called and the wax-like materials ofmineral origin.

The invention also includes the preparation of emulsions of waxes mixedwith other materials, thus, for example, it may be desirable to add afat or oily material to a paraflin wax either to reduce its meltingpoint or to impart some desired characteristic to the coating or otherfinal product.

Other oleaginous materials which I can emulsify' according to myinvention are various light fractions of petroleum; lubricating oils;vegetable oils, such as cottonseed, corn, olive and castor; hydrogenatedcastor oil; fats such as stearin; water-insoluble and difficultydispersible synthetic esters such as mannitan monostearate and mannidedipalmitate. This list is intended merely by way of example and theinvention is not limited to emulsions of these substances.

In the subloined claims the term "oil phase is used merely to indicatethe non-aqueous phase of the emulsion, in accordance with standard usagein emulsion chemistry.

The following examples illustrate the preparation of paraffin waxemulsions with an emulsifier of the present invention:

Example 5 adversel affecting the stability of the emulsion.

In this example the ratio of combined'ethylene oxide to total ester is4.8 to 1, calculated as follows from the formula set out above:

Ratio: 402x 3.5x 20 wherein Ma=402 (theory for mannitan monopalmitate)Mb=1282 (theory for mannitan monopalmitate plus 20 mols CzH40) W-=3.5Wb=3.5 12:20

Example 6 ester in 4.7 to 1 in this composition (calculated by theformula given above).

Example 7 Another good emulsifier for paraffln wax is composed of 50parts of the lipophilic reaction product of mannitol and myristic acidin a molfor-mol ratio, said product having a hydroxyl number of 351 andan ester value of 152, and 50 parts of the type B product obtained byreacting 1 mol of the said reaction product with 20 mols ethylene oxide.This final combination has a ratio of combined ethylene oxide to totalester of 4.6 to 1 (calculated by the formula given above, taking themolecular weights to be those of mannitan monomyristate and the etherthereof with 20 mols C2H4O) Example 8 An emulsifier comprising an18-carbon atom fatty acid derivative was prepared by mixing 34 parts ofthe ester of Example 2 and 66 parts of the product of Example 4. Thismixed emulsifier'had a value for the ratio of combined ethylene oxide tototal ester of 3.9 to 1 (calculated by the formula given above, takingthe molecular weights to be those of mannitan monostearate and the etherthereof with mols C2H4O).

Example 9 An emulsifier comprising an unsaturated fatty acid derivativewas prepared by mixing 50 parts of the lipoph'ilic ester produced byreacting orbitol with oleic acid in a mol-for-mol ratio, said esterhaving a hydroxyl value of 249 and an ester value 145, and 50 parts ofthe type B ether produced by reacting 1 mol of said ester with 20 molsethylene oxide. The ratio of combined ethylene oxide to total ester ofthis mixture was 4.9 to 1 (calculated by the formula given above, takingthe molecular weights to be those of mannitan monooleate and the etherthereof with 20 mols C2H4O).

Example 10 Example 11 A concentrated emulsion of a so-calledmicrocrystalline wax (Cerese Wax AA of the Socony- Vacuum Oil Co.) wasprepared by using, as the combination emulsifier, 57% of the ester ofExample 1, and 43% of the ether of Example 3. 40 parts of the wax and 7parts of emulsifier were melted together, 53 parts hot water added withagitation, and the agitation continued during cooling to roomtemperature. In this example the ratio of combined ethylene oxide tototal ester was 3.8 to 1. The emulsion was stable to dilution with hardwater.

' Example 12 A laundry wax suitable for dispersion in a hot starchsolution was prepared by melting and mixing together 35% paraflin wax,45% hydrogenated fish oil, 15% of the ester of Example 1 and 5% oftheether of Example 3. The ratio of combined ethylene oxide to total esterin this emulsiher was 1.9 to 1.

After cooling, the composition prepared as above was solid, and whendropped into a boiling starch solution, such as one used for starch'ingclothes, was found to disperse readily throughout the solution.

If desired, a dye such as a bluing can be included in a wax compositionprepared as in the foregoing example.

The invention is not limited to the use of esters and ethers containingthe same fatty acid nor is it limited to esters and ethers with the samepolyhydroxylic residue.

Example 13 An emulsifier for paraifin wax was prepared by mixingtogether 50 parts of the ester of Example 2 and 50 parts of the eth'erof Example 3. This composition had a value for the ratio combinedethylene oxide to total ester of 5.03 to 1.

The invention is not limited to the emulsifiers or the emulsions of thepreceding examples but such are given merely for the guidance of thoseskilled in the art so that they can practice the invention. An emulsionsuch as that prepared in accordance with Example 5 can be used to sprayon to paper stock, fabric, or the like for the purpose of modifying th'esurface thereof and decreasing absorbency. Because of its stability todilution with hard water the emulsion can be marketed in a. concentratedform and can be diluted with ordinary unsoftened water at the place ofuse. Such stability is of ve ygreat advantage as will be apparent.

In some usages it is possible to reduce the amount of emulsifier; such,for instance, is the case where the emulsion can conveniently be keptagitated. For example, it may be desired to impregnate paper fibres inthe beater and in such a case the quantity of emulsifier necessary tokeep the wax suspended would be less than in the case where the waxemulsion was to be stored in a quiet condition and applied by spraying aportion withdrawn from time to time.

The concentrated parafiin wax emulsions produced by the aid of mycombination emulsifier are stable, and may be diluted with hard waterwithout loss of emulsion stability. Such diluted emu; sions can be usedvery conveniently for wet waxing of paper, textiles, and the like. Onlong storage, however, particularly when agitated, there is a slighttendency for a small proportion of the wax to crystallize out from thedisperse phase, in small,thin flakes. This effect, whose rate tends toincrease with increasing hardness of the diluting water, is entirelydifferent from a true breaking of the emulsion. An imperfect emulsionbreaks down to give a curdy, flocculent precipitate, entirely differentin ph'ysical character, ease of removal, and technical significance fromthe wax crystallization.

I have found that the wax separation, when undesirable, can beprevented, or reduced to the point at which it is no longer of practicalimportance, by the further addition of certain surface active agents tothe freshly-made dilution, or to the concentrated emulsion immediatelybefore dilution. For this, certain alkyl aryl sodium sulfonates, anddialkyl sulfosuccinates, particularly dioctyl sodium sulfosuccinate havebeen found useful.

In the case of the substituted aryl sodium sulfonates, such as theproduct sold by we National Aniline & Chemical Co. under the trade-markNacconol NRSF, the amounts needed depend on the hardness of the waterused and the degree of crystallization suppression desired, and may beas much as that of the A+B combination.

The dioetyl sodium sufosuccinate is effective over a range ofconcentrations, but works best at about 15% of A+B. It may be added inthe dry state, or conveniently as a concentrated solution, the usualform in which it is marketed. Thus,

is diluted sevenfold by addition of water containing 50 P. P M. ofcalcium chloride, or an equivalent amount of calcium ions, addition of 1part of dioctyl sodium sulfosuccinate per 7 parts of A+B to the finisheddilution confers satisfactory stability against wax separation, evenwhen shaken.

The following tabulation is oirered by way of examples of thepreparation of emulsions with oil phases of various types. Severalfurther emulsifier combinations are also shown in these examples. Ingeneral the emulsions were prepared by simply mixing the emulsifier withthe oil phase (melted if necessary) and then adding the water (at aboutthe same temperature) with stirring meanwhile. The emulsions of theseexamples were very readily prepared and showed useful properties. Theyexhibited variations in viscosity, particle size, behavior on dilution,stability in storage, etc, as would be expected. This method ofpreparing my emulsions is much easier than that required'to prepareemulsions using a soap when the concentrated emulsion of Example 5 orspecial milling procedure.

Parts Parts Example Oil phase of oil of A-type emulsifier Parts B-typeemulsifier Parts g g phase water Stearin 40 53 Prod. Ex. 1 Prod. Ex. 33. 5 O/W. Beeswax. 40 153 do .....do 3.5 0/W. -----d0 40 53 do 3.5 O/Wsolid cold. M a id dipalml- 4o 53 ..do 3.5 O/W.

a e. Refined mineral oil.. 40 53 Sorbitan mononaphthe- 3. 5 O/W.

n e. Mineral seal oil..... .40 53 Sorbitan(1)monolaurate.. 3.5 Sorbitan(1) monolaurate re- 3.5 O/W.

actgd with 20 mols ethylene on e. 20 Cottonseed Oil 40 53 Sorbitan (2)monooleate-.. 3.5 Sorbltan (2) monooicate re- 3. 5 O/W.

acted with 20 mols ethylene 40 53 Prod. Ex. 1 3. 3. 5 O/W. Castor oil 4063 3. 3.5 O/W. Hydroglenated 40 53 3, 3.5 O/W.

ore Olive oil 40 53 Sorbitan (1) monolaurate 3.5 Sorbitan (1)monolauratc to- 3.5 0/W. aotedd with 20 mols ethylene 3. 5 O/W. ox e.White mineral oil 40 53 Prod. Ex. 1 3. 5 Prod. Ex. 3 3.5 O/W (65 sec.Say.). 26 Nephthenic acid so 150 do 7.0 .do 7.0 O/W (commercial,apparent molecular weight 282). 27 Naphthenic acid v 150 Sorbitan (1)monolaurate. 7.0 Sorbitan (l) monolaurate re- 7.0 O/W.

(commercial, apacted with 20 mols ethylene parent molecular oxide.weight 191). Scale paraffin Wax... 80 106 Prod. Ex. 1 3. 5 Prod. Ex. 33. 5 O/W. ..do 2o 27 o 3.5 o, 3.5 0/W. Paraflin base oil.... 900Sorbitan (l) mono urate. 7. 5 Mannitan monooleate reacted 7. 5 CAN.

with 16 mols of ethylene O/W oxide. (3) d0 85 900 Mannitan (3)monooleate 3. 75 Mannitan monooleate reacted 11.25 O/W.

with 12 mols of ethylene oxide. 32 do 85 900 Monolaurates ofmannitan 7.5Mannitan dilaurate eacted 7.5 0/W.

and glycerol (4). with 1?. mols of ethylene oxide. r Refined mineraloil. 56 40 Prod, Ex. 1 2. 0 Prod. Ex. 3 2.0 0/ Mineral seal oil 50 119Sorbitan (1) monolaurate.. 12.0 Sorbitan monolaurate reacted 19.0 O/W.

with 20 mols of ethylene oxide. (1) Sc e WflX 40 53 Glycerolmonopalmltate... 3. 5 Prod Ex. 3 3- 5 0/W. Orange Oil 40 53Sorbitanmonolaurate (1).. 3.5 Sorbitan (1) monolaurate.re- 3.5 O/W.

acted with 20 mols ethylene oxide. 7 37.... Benzene 40 53 Prod. Ex. 1 3.5 Prod. Ex. 3 3.5 O/

(1) Sorhitan monolaurate is the lipophilic reaction product of 1 molsorbitol and 1 mol commercial lauric acid under conditions analogous toExample 1, supra.

(2) Sorbitan monoleate is the lipophliic reaction product of 1 molsorbitol and 1 mol commercial oleic acid under conditions analogous toExample 1, supra.

(3) Mannitan monoolcate is the lipophilic reaction product of 1 molmannitul and 1 mol commercial olcic acid under conditions analogous toExample 1, supra.

(4) Monolauratcs the roduct consisting chieliy of about 2 mols manuitanmonolaurate 5) Mann tandiluurate is the lipophilio reaction product of 1mol to Example 1, supra.

of mannitan and glycerol is the lipophilic reaction product of and 1 molglycerol monolaurate. mannitol and 2 mols commercial launc acid underconditionsanalogous the alcoholysis of 1 mol coconut oil with 2 molsmannitol,

( Sorbitan mononaphthenate is the lipophilic reaction product of 1 molSorbitoi and 1 mol naphthcnic acid (apparent molecular weight 191) underconditions analogous to Example 1, supra.

Many of the emulsions prepared according to the invention show markedresistance to breaking in the presence of electrolytes. The emulsion ofExample 32, for example, can be made with water having a hardness of2000 parts per million as CaCOa and still has good stability. Theemulsion of Example is extremely resistant to electrolytes and 1 part ofthe concentrated emulsion can be diluted with nine parts 10%hydrochloric acid or 10% potassium hydroxide without destroying theemulsion.

The invention has been described and illustrated by a number ofexamples, but it is to be understood that it is subject to manyvariations without departing from its spirit. The invention, is,therefore, to be limited only by the scope of the following claims.

I claim:

1. An emulsifier comprising the mixture of a. lipophilic partial esterof a long chain fatty acid and a hydrophilic polyhydroxylic organiccompound, and a highly hydrophilic hydroxypolyoxyethylene ether of alipophilic partial ester of a long chain fatty acid and a hydrophilicpolyhydroxylic organic compound, said hydroxypolyoxyethylene ethercontaining at least 10 oxyethylene groups; said partial ester andhydroxypolyoxyethylene ether being present in the mixture in suchproportions that the ratio of oxyethylene groups in saidhydroxy-polyoxyethylene ether to the total ester groups (both in thefree ester and in the hydroxy-polyoxyethylene ether) is in the range offrom about 1.5 to 9.0.

2. An emulsifier comprising the mixture of a lipophilic partial ester ofa long chain fatty acid and a hydrophilic compound selected from thegroups consisting of polyhydric alcohols, polyhydroxylic cyclic innerethers of polyhydric alcohols, polyhydroxylic external ethers ofpolyhydric alcohols, and polyhydroxylic external ethers ofpolyhydroxylic cyclic inner ethers of polyhydric alcohols; and a highlyhydrophilic hydroxy-polyoxyethylene ether of a lipophilic partial esterof a long chain fatty acid and a. hydrophilic compound selected from thesaid groups, said hydroxy-polyoxyethylene ether containing at least 10oxyethylene groups; said partial ester and said hydroxy-polyoxyethyleneether being present in the mixture in such proportions that'the ratio ofoxyethylene groups in said hydroxy-polyoxyethylene ether to the totalester groups (both in the free ester and in the hydroxy-polyoxyethyleneether) is in the range of from about 1.5 to 9.0.

3. An emulsifier comprising the mixture of a partial ester of apolyhydroxylic cyclic inner ether of a hexitol and a fatty acid of atleast 12 carbon atoms; and a highly hydrophilic hydroxypolyoxyethyleneether of a lipophilic long chain fatty acid partial ester of a compoundselected from the group consisting of polyhydric alcohols, thepolyhydroxy cyclic inner ethers of polyhydric alcohols, polyhydroxyexternal ethers of polyhydric alcohols, and polyhydroxy external ethersof polyhydroxy cyclic inner ethers of polyhydric alcohols, thecombination having a ratio of oxyethylene groups in the saidpolyoxyethylene ether to the total ester groups (both in the free esterand in the polyoxyethylene ether) of from about 1.5 to 9.0.

4. An emulsifier comprising the mixture of a partial ester of apolyhydroxylic cyclic inner ether of a hexitol and a fatty acid with atleast 12 carbon atoms; and a highly hydrophilic hydroxy-polyoxyethyleneether of a partial ester of ass mo a polyhydroxylic cyclic inner etheror a hexitol and a fatty acid with at least 12 carbon atoms; the mixturehaving a ratio of oxyethylene groups in the said polyoxyethylene etherto the total ester groups (both in the free ester and in thepolyoxyethylene ether) of from about 1.5 to 9.0.

5. An emulsifier comprising the mixture of a lipophilic partial ester01' a polyhydroxylic cyclic inner ether of a hexitol and a fatty acid ofat least 12 carbon atoms, the ratio hydroxyl value to ester value in thesaid partial ester being from about 3 to 1; and a highly hydrophilichydroxypolyoxyethylene ether of a lipophilic long chain fatty acidpartial ester of a compound selected from the group consisting ofpolyhydric alcohols, the polyhydroxy cyclic inner ethers of polyhydricalcohols, polyhydroxy external ethers of polyhydric alcohols, andpolyhydroxy external ethers of polyhydroxy cy clic inner ethers ofpolyhydric alcohols, the combination having a ratio of oxyethylenegroups in the said polyoxyethylene ether to the total ester groups (bothin the free ester and in the polyoxyethylene ether) of from about 1.5 to9.0.

'6. An emulsifier comprising the mixture of a lipophilic partial esterof a polyhydroxylic cyclic inner ether of a hexitol and a fatty acidwith at least 12 carbon atoms, the ratio hydroxyl value to ester valuein said partial ester being from about 3 to 1; and a highly hydrophilichydroxypolyoxyethylene ether of a lipophilic partial ester of apolyhydroxylic cyclic inner ether of a hexitol and a fatty acid with atleast 12 carbon atoms, said polyoxyethylene ether containing from about10 to 30 oxyethylene groups; and the mixture having a ratio ofoxyethylene groups in the said polyoxyethylene ether to the total estergroups (both in the free ester and in the polyoxyethylene ether) of fromabout 1.5 to 9.0.

7. A composition for emulsifying hard paraflin waxes and water,comprising the mixture of a lipophilic partial ester of a fatty acidwith at least 12 carbon atoms and a, polyhydroxylic cyclic inner etherof a hexitol, the ratio hydroxyl value to ester value in the saidpartial ester being from about 3 to 1.5; and a highly hydrophilichydroxypolyoxyethylene ether of a lipophilic partial ester of a fattyacid with at least 12 carbon atoms and a polyhydroxylic cyclic innerether of a hexitol, said polyoxyethylene ether containing from about 10to 30 oxyethylene groups; the composition having a ratio of oxyethylenegroups in said polyoxyethylene ether to the total ester groups (both inthe free ester and in the polyoxyethylene ether) of from about 4 to 5.

8. An emulsifier comprising the mixture of a partial palmitic acid esterof cyclic inner ether of mannitol, which ester consists largely ofmannitan monopalmitate; and a highly hydrophilic hydroxy-polyoxyethyleneether of said ester containing about 20 oxyethylene groups; thecombination having a ratio of oxyethylene groups in said polyoxyethyleneether to total ester groups (both in the free ester and in thepolyoxyethylene ether) of from about 1.5 to 9.0.

9. An emulsion comprising an oil phase; water; and a mixed emulsifiercomprising a lipophilic partial ester of a long chain fatty acid and ahydrophilic compound selected from the roup consisting of polyhydricalcohols, polyhydroxylic cyclic inner ethers of polyhydric alcohols,polyhydroxylic external ethers of polyhydric alcohols, andpolyhydroxylic external ethers of polyhydroxylic cyclic inner ethers ofpolyhydric alcohols, and a hig y hydrophilic hydroxy-P Y- ether to totalester groups (both in the free ester and in the hydroxy-polyoxyethyleneether) being from about to 9.0. 10. Ari eijriulsion comprising wax;water; and

a mixed emulsifier comprising a lipophilic partial ester of a fatty acidwith at least 12 carbon atoms and a hydrophilic compound selected fromthe group consisting of polyhydric alcohols, polyhydroxylic cyclic innerethers of polyhydric alcohols, polyhydroxylic external ethers ofpolyhydric alcohols, polyhydroxylic external ethers of polyhydroxyliccyclic inner ethers of polyhydric alcohols, and a highly hydrophilichydroxy-polyoxyethylene ether of a lipophilic partial ester of a fattyacid with at least 12 carbon atoms and a hydrophilic compound selectedfrom the said group, said hydroxy-polyoxyethylene ether containing fromto 30 oxyethylene groups, and the ratio of the oxyethylene groups in thehydroxy-polyoxyethylene ether to total ester g oups (both in the freeester and in the hydroxy-polyoxyethylene ether) being from about 1.5 to9.0.

11. An emulsion comprising an oil phase, water, and a combinationemulsifier comprising the combination of a lipophilic partial ester of apolyhydroxylic cyclic inner ether of a hexitol, and a fatty acid of atleast 12 carbon atoms, the ratio hydroxyl value to ester value in saidpartial ester being from about 3 to 1, and a highly hydrophilichydroxy-polyoxyethylene ether of a partial long chain fatty acid esterof a compound selected from the group consisting of polyhydric alcohols,the polyhydroxy cyclic inner ethers of polyhydric alcohols, polyhydroxyexternal ethers of polyhydric alcohols, and polyhydroxy external ethersof polyhydroxy inner ethers of polyhydric alcohols, said polyoxyethyleneether containing from about 10 to 30 oxyethylene groups, the combinationhaving a ratio of oxyethylene groups in the polyoxyethylene ether tototal ester groups (both in the free ester and in the polyoxyethyleneether) of from about 4 to 5.

12. An emulsion comprising wax, water, and a combination emulsifiercomprising the combination of a lipophilic partial ester of apolyhydroxylic cyclic inner ether of a hexitol, and a fatty acid of atleast 12 carbon atoms, the ratio hydroxyl value to ester value in saidpartial ester being-from about 3 to 1, and a highly hydrophilichydroxy-polyoxyethylene ether of a partial long chain fatty acid esterof a compound selected from the group consisting of polyhydric alcohols,the polyhydroxy cyclic inner ether of polyhydric alcohols, polyhydroxyexternal ethers of polyhydric alcohols, and polyhydroxy external ethersof polyhydroxy inner ethers of polyhydric alcohols, said polyoxyethyleneether containing from about 10 to 30 oxyethylene groups, the combinationhaving a ratio of oxyethylene groups in the polyoxyethylene ether to thetotal ester groups (both in the free ester andin the polyoxyethyleneether) of from about 1.5 to 9.0.

13. An emulsion comprising paraflln wax; water; and a mixed emulsifiercomprising a lipophilic partial ester of a fatty acid with at least 12carbon atoms and a polyhydroxylic cyclic inner ether of a hexitol, saidester having a ratio hydroxyl value to ester value of from about 3 to1.5, and a highly hydrophilic hydroxy-polyoxyethylene ether of alipophilic partial ester having a ratio hydroxyl value to ester value offrom about 3 to 1.5 and being an ester of a fatty acid with at least 12carbon atoms and a polyhydroxylic cyclic inner ether of a hexitol, saidhydroxy-polyoxyethylene ether containing from 10 to 30 oxyethylenegroups, and the mixed emulsifier having a ratio of oxyethylene groups inthe polyoxyethylene ether to total ester groups (in both the free esterand the polyoxyethylene ether) of from about 4 to 5.

14. An emulsion in accordance with claim 13 and further containing aproportion of dioctyl sodium sulfosuccinate sufficient to inhibit waxcrystallization on dilution of the emulsion with hard water.

15. An emulsion comprising an oil phase, water, and a combinationemulsifier comprising a partial palmitic acid ester of cyclic innerether of mannitol, which ester consists largely of mannitanmonopalmitate, and a highly hydrophilic hydroxy-polyoxyethylene ether ofsaid ester containing about 20 oxyethylene groups, said combinationhaving a ratio of oxyethylene groups in the polyoxyethylene ether tototal ester groups (both in the free ester and in the polyoxyethyleneether) of from about 1.5 to 9.0.

16. An emulsion comprising wax, water, and a combination emulsifiercomprising a partial palmitic acid ester of cyclic inner ether ofmannitol, which ester consists largely of mannitan monopalmitate, and ahighly hydrophilic hydroxy-polyoxyethylene ether of said ester containing about 20 oxyethylene groups, said combination having a ratio ofoxyethylene groups in the polyoxyethylene ether to total ester groups(both in the free ester and in the polyoxyethylene ether) of from about1.5 to 9.0.

17. An emulsion concentrate comprising by Weight paraffin wax about 40parts; water about 53 parts; about 3.5 parts of a partial palmitic acidester of cyclic inner ether of mannitol, which ester consists largely ofmannitan monopalmitate, and about 3.5 parts of a hydroxy-polyoxyethyleneether of said ester containing about 20 oxyethylene groups, saidemulsion being capable of dilution with hard water without breaking.

18. An emulsion comprising an oil phase, water and a mixed emulsifiercomprising a lipophilic partial ester of a long chain fatty acid and ahydrophilic polyhydroxylic organic compound, and a highly hydrophilichydroxy-polyoxyethylene ether of a lipophilic partial ester of a longchain fatty acid and a hydrophilic polyhydroxylic organic compound, saidhydroxy-polyoxyethylene ether containing at least 10 oxyethylene groups;said partial ester and said hydroxy-polyoxyethylene ether each beingpresent in a substantial amount in the said mixed emulsifier and theratio of oxyethylene groups in the hydroxypolyoxyethylene ether to totalester groups (both in the free ester and in the hydroxy-polyoxyethyleneether) being from about 1.5 to 9.0.

WILLIAM C. GRIFFIN.

